Zheng Raojun, Binks Bernard P, Cui Zhenggang
Department of Chemistry and Biochemistry, University of Hull, Hull HU6 7RX, U.K.
The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, P. R. China.
Langmuir. 2020 May 5;36(17):4619-4629. doi: 10.1021/acs.langmuir.0c00261. Epub 2020 Apr 21.
At high pH, bare silica particles are not an effective Pickering emulsion stabilizer of nonpolar oils with water due to their high surface charge. One way to promote particle adsorption to the oil-water interface is to add salt to the aqueous phase, although particle flocculation normally ensues. In most cases, inorganic salts are added, while little attention has been paid to the use of organic salts. Here, we describe the effects of adding tetraalkylammonium salts (RNX, X is an anion) to aqueous dispersions of silica nanoparticles at high pH and investigating the possibility of subsequently stabilizing octane-in-water (o/w) emulsions. The chain length of the R group is systematically increased from 1 (methyl) to 4 (butyl). Unlike inorganic electrolytes, the addition of these salts does not lead to particle flocculation in water, although the particle charge is reduced. No stable emulsion forms for the methyl analogue, but very stable o/w emulsions can be prepared with the other three members, with the minimum concentration of salt being required decreasing with R chain length to as low as 5 × 10 M. The three-phase oil-water-solid contact angle increases with salt concentration and R chain length, confirming the increase in particle hydrophobicity on addition of salt. We show that the butyl analogue behaves similarly to that of cetyltrimethylammonium bromide surfactant with respect to promoting silica particles to emulsion drop interfaces. Finally, we compare the arrangement of micrometer-sized silica particles at both curved droplet interfaces and at a planar oil-water interface at different concentrations of the most hydrophobic salt.
在高pH值下,由于裸露的二氧化硅颗粒表面电荷较高,它们并不是非极性油与水形成皮克林乳液的有效稳定剂。促进颗粒吸附到油水界面的一种方法是向水相中添加盐,不过通常会随之发生颗粒絮凝。在大多数情况下,添加的是无机盐,而对有机盐的使用关注较少。在此,我们描述了在高pH值下向二氧化硅纳米颗粒的水分散体中添加四烷基铵盐(RNX,X为阴离子)的效果,并研究了随后稳定水包辛烷(o/w)乳液的可能性。R基团的链长从1(甲基)系统地增加到4(丁基)。与无机电解质不同,添加这些盐不会导致水中颗粒絮凝,尽管颗粒电荷会降低。甲基类似物不会形成稳定的乳液,但其他三种可以制备出非常稳定的o/w乳液,所需盐的最低浓度随着R链长度的增加而降低,低至5×10⁻³M。三相油水 - 固体接触角随着盐浓度和R链长度的增加而增大,证实了添加盐后颗粒疏水性的增加。我们表明,丁基类似物在促进二氧化硅颗粒吸附到乳液滴界面方面的行为与十六烷基三甲基溴化铵表面活性剂类似。最后,我们比较了在不同浓度的最疏水盐存在下,微米级二氧化硅颗粒在弯曲液滴界面和平面油水界面处的排列情况。